1,1,4,4-Tetra methyl-alkyl-nitriles-tetrahydronaphthalene perfume compositions

ABSTRACT

The 1,1,4,4-tetramethyl-alkyl-nitrile-tetrahydronaphthalenes and the perfume compositions containing them have striking odor intensities of high tenacity resembling the odors of natural musk. They do not discolor when applied as perfume material per se or when utilized in combination with other aroma chemicals in cosmetics, soaps or household products.

United States Patent [191 111] 3,910,853 Kulka Oct. 7, 1975 [5 1,1,4,4-TETRA 3,769,348 10/1973 Wood 252/522 METHYL-ALKYL-NlTRlLES-TETRAHY- DRONAPHTHALENE PERFUME COMPOSITIONS [75] Inventor: Kurt Kulka, New York, N.Y.

[73] Assignee: Fritzsche Dodge & Olcott Inc., New

York, N.Y.

[22] Filed: July 29, 1974 [21] Appl. No.: 492,521

[52] U.S. Cl. 252/522; 260/465 R [51] Int. Cl. CllB 9/06 [58] Field of Search 252/522; 260/465 R [56] References Cited UNlTED STATES PATENTS 2,800,5l l 7/1957 Carpenter et ai 252/522 Primary Examiner-Veronica OKeefe Attorney, Agent, or FirmFrank M. Nolan [57] ABSTRACT The l ,1,4,4-tetramethyl-alkyl-nitrile-tetrahydronaphthalenes and the perfume compositions containing them have striking odor intensities of high tenacity resembling the odors of natural musk. They do not discolor when applied as perfume material per se or when utilized in combination with other aroma chemicals in cosmetics, soaps or household products.

3 Claims, N0 Drawings l,l ,4,4-TETRA' The reaction which takes place is. indicated in the fol- METHYL-ALKYL-NITRlLES-TETRAHY- lowing action scheme:

DRONAPHTHALENE PERFUME COMPOSITIONS This invention relates to l,l,4,4-tetramethylealkylnitrile-tetrahydronaphthalenes and perfume com'posi- 5 tions containing them.

Natural musk is derived from the Asian Musk Deer. Natural must has two characteristic odors. One is a sweet musk odor; the other is sweaty animal odor. Strange as it may appear, both are essential for obtain- AlCl3 ing the unique musk-like odor. Natural musk is ex- 2 Hcl tremely expensive because of the limited quantity avail- 1 able. By utilization of the nitriles of this invention, both R characteristics of natural musk are achieved.

In accordance with a feature of thisinvention, l,l,4,- in which R is methyl 'or ethyl.

4-tetramethyl-alkyl-nitrile-tetrahydronaphthalenes are The resulting l,1,4,4-tetramethyl-6-alkyl-l,2,3,4-tetutilized instead of the expensive natural musk as a perrahydronaphthalene is chloromethylated with parafume. The compounds of this invention are novel and formaldehyde and hydrochloric acid in the presence of have the following formula: glacial acetic acid and phosphoric acid to produce 1,1

4,4tetramethyl-6-alkyl-7-chloromethyl-tetrahydronaphthalene in accordance with the following reac- CN tion:

R Y 2 )n HCl (Chloromethylation) cH c1 in which R is methyl or ethyl.

The l ,l ,4,4-tetramethyl-alkyl-nitrile-tetrahydronaphthalenes of this invention have strikingly natu- R ral musk-like odors. The nitriles of this invention are several times more potent in their odor intensities than The resulting m yl- -alkyl-7- the corresponding aldehydes described in U.S. Pat. No. hloromethyltetrahydronapthalene is then reacted 2,8005] 1 granted on J l 23, 1957 to h assignee f with Z-nitropropane and sodium methoxide in metha- M, S. Car ent r et al, In addi i n, th d r d r ti f nol solution. An exothermic reaction takes place. After the nitriles of this invention is several times greater the COmPICtiOH Of he r a tion, water and benzene are than that of the aldehydes. The nitriles also have a high 40 added- The ulting miXture is then separated into an tenacity. Besides their basic musk odor, the nitriles g ni part and an aqueous part. The Organic part is h v d i bl b Th bymote f th diwashed successively with a 5% sodium hydroxide solul d i il may b d ib d as l Sweettion followed by two washings with water. The benzene musty". Further, the nitriles of this invention are stable. is removed y ati n and the reaction product so- They do not discolor when applied as perfume materilidified- The resulting Product y be recystallized als per 5 or when utilized in combination with ther from a suitable solvent SUCh as methanol. 16 reaction aroma chemicals in cosmetics, soaps, household prodwhich takes p e is as follows:

ucts or in alcohol solutions such as perfumes or colognes. ln contract, aldehydes are relatively unstable under such conditions. They are prone to air oxidation and chemical changes are possible in alkaline or acid media.

In accordance with another feature of this invention, the novel nitriles can be advantageously utilized in the production of perfume compositions. Such compositions contain at least by weight of the novel nitriles, and at least 1% by weight of a component which modities the olfactory properties of the nitriles. In dilution, the nitriles exhibit a more flowery musk main-odorx theme, with an animal and a slight but pleasant by-note. s C NOH NaCl These characteristics are particularly manifested in the cH'o H,

. ll compositions containing one or both novel nitriles with other perfume compositions. v I g The compositions of this invention are produced, for i 7 example, by initially reacting 2,5-dimethyl-2,5- The l,1,4,4-tetramethyl-6-alkyl-7-formyldichlorohexane with either toluene or ethylbenzene in tetrahydronaphthlene formed is reacted with hydrolxthe presence of a catalyst such as aluminum chloride. ,yamine hydrochloride dissolved in water. Desirably the reaction mixture is agitated for a period of about 5 minutes, after which a solution of sodium hydroxide is added. After agitation for about 3 hours, the reaction mixture is cooled by the addition of shaved ice. The reaction mixture is then saturated with carbon dioxide by the gradual addition of solid carbon dioxide. The mixture is permitted to stand-for several hours, for example overnight. The reaction which takes place is as follows:

The resulting l ,1 ,4,4-tetramethyl-6-alkyl-7-aldoxime tetrahydronaphthalene is reacted with acetic anhydrid e. The'mixture is agitated and gradually heated over a period of about minutes, to about 123C. It is then refluxed for 1 hour. The reaction mixture is then permitted to cool to room temperature and a mixture of water and benzene is added. The reaction product in benzene solution is then washed successively 3 times with water, twice with aqueous sodium carbonate solution, once with aqueous sodium bicarbonate solution and finally with water. The solvent is removed by distillation and the product recrystallized by a suitable solvent such as methanol. The reaction which takes place is as follows:

' CH=NOH (CH3C0) o -9 R 2CH3COOH R A more comprehensive understanding of this invention is obtained by reference to the following examples:

EXAMPLE I l ,1 ,4,4,6-Pentamethyl-7-Nitrile-Tetrahydronaphthalene To produce the starting material l,l,4,4,6-

iod of 4 hours to 60 (maximum temperature) and then permitted to come to room temperature. To the reaction mixture was added under agitation at room temperature 6000 ml of a 5% aqueous hydrochloric acid solution. The aqueous part was separated from the organic part. The organic part was washed successively with 3000 ml of water, 3000 ml of a saturated aqueous sodium carbonate solution, 3000 ml of a saturated aqueous sodium bicarbonate solution and 3000 ml of water. The excess toluene was recovered by distillation through a 14-inch column packed with glass rings, at an ejector vacuum and the desired reaction product was obtained by fractionation at 4 mm pressure, boiling at 95-97C. The yield of the l,l,4,4,6-pentamethyl-tetrahydronaphthalene was 4228 g, (4500 ml).

1 ,1 ,4,4,6-pentamethyL7-chloromethyl-tetrahydronaphthalene was produced by mixing in a reaction flask with agitation 1212 g of l,l,4,4,6-pentamethyltetrahydronaphthalene, 440 g of paraformaldehyde, 1090 g of glacial acetic acid, 1058 g of phosphoric acid and 1712 g of concentrated hydrochloric acid. The agitated reaction mixture was gradually heated over a period of 3 hours to 102C and kept at this temperature under agitation for a period of 8 hours. There was added to the warm solution (approximately 50C) 1500 ml of benzene and 2000 ml of water. The organic part was separated and washed successively with 1500 ml of aqueous saturated sodium carbonate solution, 1500 ml of aqueous saturated sodium bicarbonate solution and 1500 ml of water. The solvent was removed from the reaction mixture by distillation through a /2 ft Vigreux column at an ejector vacuum. The desired 1,1- ,4,4,6-pentamethyl-7-chloromethyl-tetrahydronaphthalene was obtained by fractional distillation at 2 mm vacuum boiling at l28130C. The product solidified. The yield of 1,1,4,4,6-pentamethyl-7-chloromethyl-tetrahydronaphthalene was 1322 g (1300 ml) having a melting point of 7881C.

The 1,1 ,4,4,6-pentamethyl-7-chloromethyl-tetrahydronaphthalene is utilized to produce l,l,4,4,6- pentamethyl-7-formyl-tetrahydronaphthalene. Initially there was dissolved 20.7 g of sodium (metal) in 300 ml of methanol. To this solution was added 101 g of 2- nitropropane at a temperature of 55C. An exothermic reaction resulted with the temperature rising to 60C. To the resulting reaction mixture was added 187.5 g of l ,1 ,4,4,6-pentamethyl-7-chloromethyltetrahydronaphthalene with agitation over a period of 1 hour. An exothermic reaction resulted and the reaction mixture started to reflux. The exotherm gradually subsided at 27C after a 4-hour period of agitation. The methanol was distilled off under agitation. To the reaction mixture was added 400 ml of water and 300 ml of benzene. The mixture was separated into an organic part and an aqueous part. The organic part was washed three times with 200 ml of 5% aqueous sodium hydroxide solution, followed by two washings with 200 ml of water. The solvent. benzene, was removed by distillation and the reaction product solidified. It was recrystallized from 150 ml of methanol. The yield was 139 g with a melting point of 84-86C.

The oxime of 1,1,4,4,6-pentamethyl-7-formyl-tetrahydronaphthalene was produced by initially preparing a solution of 230 g of 1,1 ,4,4,6-pentamethyl-7- formyl-tetrahydronaphthalene in 500 ml of ethanol at a temperature of 50C. To the 95 ethanol solution was added under agitation in one portion 82.8 g of hydroxylamine hydrochloride dissolved in .100 ml of water. To the resulting solution of hydroxylamine hydrochloride was added under agitation during a period of about 5 minutes a solution of 60 g of sodium hydroxide in 80 ml of water. An exothermic reaction resulted, the reaction temperature rising to 72C. After agitation for 3 hours, the temperature of the reaction mixture declined to 28C. To cool the mixture, 500 g of shaved ice was added. The temperature of the reaction mixture dropped to 2C. The reaction mixture was then saturated with carbon dioxide by the gradual addition of 250 g of dry ice. The reaction mixture decreased to 15C during a minute period. It then rose gradually to C during the following 3 hours. It was then permitted to stand overnight. The solid oxime (aldoxime) was collected on a Buchner funnel and washed 4 times with 100 ml of water followed by two washings with 100 ml of hexane. The yield was 240 g-of l,l,4,4,6- pentamethyl-7aldoxime-tetrahydronaphthalene having a melting point of 148-l40C.

To produce the corresponding nitrile, 200 g of 1,1 ,4,- 4,6-pentamethyl-7aldoximetetrahydronaphthalene were mixed with 200 g of acetic anhydride. The mixture was agitated and gradually heated over a period of 15 minutes to 120C. The reaction mixture was then refluxed for 1 hour, and then permitted to come to room temperature. There were added 400 ml of water and 300 ml of benzene. The organic part was then washed 3 times with 150 ml of water followed by twice washing with 150ml of aqueous sodium carbonate solution, followed by one washing with 150 ml of aqueous sodium bicarbonate solution and finally with 150 ml of water. The solvent, benzene, was removed by distillation. The product solidified. There were obtained 176 g of the crude product. The product was recrystallized from methanol. A yield of 145 g of 1,l,4,4,6- pentamethyl-7nitrile-tetrahydronaphthalene having a melting point of l24l 25C was obtained.

EXAMPLE ll 1 ,1 ,4,4,-Tetramethyl-6-Ethyl-7-Nitrile-Tetrahydronaphthalene To produce the starting material 1,1 ,4,4,- tetramethyl6-ethyl-tetrahydronaphthalene, an agitated mixture of 1484 g of ethylbenzene and 30 g of ferric chloride was added under cooling, keeping the reaction mixture at 5C over a period of one hour, a solution of 732 g of 2,5diniethyl-2,5-dichlorohexane and 1272 g of ethyl benzene. After completion of the addition, agitation was continued at 4C over a period of 3 hours. The reaction mixture was poured over 1400 g of ice containing 60 g of concentrated hydrochloric acid. The organic part was separated from the aqueous part and the organic part was washed twice with 500 ml of water followed by a single washing successively with 500 ml of saturated sodium carbonate solution, 500 ml of saturated sodium bicarbonate solution and 500 ml of water. The unreacted excess ethyl-benzene was recovered by fractionation from a steam bath and an ejector vacuum through a 14 inch column, packed with glass rings. The reaction product was fractionated at ll.5 mm pressure boiling at 83-86C. The yield was 754 g of 1,1 ,4,4-tetramethyl-6-ethyl-tetrahydronaphthalene.

1 1',4,4-tetramethyl 6ethyl-7-chloromethyl-tetrahydronaphthalene was then produced by adding to a reaction flask and agitating the following:

648 g of l,l,4,4-tetramethyl6-ethyl-tetrahydronaphthalene I 220 g of paraformaldehyde 545 g of glacial acetic acid 336 g of 85% phosphoric acid 856 g of concentrated hydrochloric acid.

The reaction mixture was heated to 98100C over a period of 24 hours. The G. L. C. examination indicated that 80% had reacted. Hydrogen chloride gas was then introduced into the reaction mixture at 6870C for l /ahou'rs. The reaction mixture was then permitted to cool and 1500 ml of water and 750 ml of hexane were added. The reaction mixture was agitated for 10 minutes, permitted to set and separated into an organic part and an agueous part. The organic part was washed twice with 500 ml of water followed by a single washing in 500 ml of saturated sodium carbonate solution, 500 ml of saturated sodium bicarbonate solution and 500 ml of water. The solvent, hexane, was removed by distillation under an ejector vacuum. The reaction product was fractionated through a V2 foot Vigreux column at a 1 mm vacuum, boiling at 1 17-1 19C. It solidified. The yield was 618 g of 1,1,4,4-tetramethyl-6ethyl-7 -chloromethyl-tetrahydronaphthalene having a melting point of 66C.

The 1 1 ,4,4-tetramethyl-6-methyl-7-chloromethyltetrahydronaphthalene is utilized to produce l,l,4,4- tetramethyl-6-ethyl-7formyl-tetrahydronaphthalene. Initially, 57.5 g of sodium(meta1) were dissolved in 800 'ml of methanol. An oxothermic reaction resulted. To

this solution was added at a temperature of 55C 267 g of 2-nitropropane. An exothermic reaction resulted with the temperature rising to 65C. There were then added under agitation over a period of 15 minutes 528 g of 1 ,1 ,4,4-tetramethy1-6-ethyl-7-chloromethyl-tetrahydronaphthalene. The temperature rose to C under reflux. Continued agitation and heat were applied to reflux at 70C. The methanol was removed by distillation under agitation. To the crude reaction product was added 1000 ml of water and 500 ml of hexane. The mixturewas agitated for 5 minutes and the aqueous part and the organic part were separated. The organic part was successively washed with 500 ml of water, 500 ml of a 5% sodium hydroxide aqueous solution, 500 ml of a saturated sodium bicarbonate aqueous solution, and 500 ml of water. The solvent, hexane, was removed by distillation through a /2 ft Vigreux column at 1 mm pressure. The yield of l,l,4,4,-tetramethyl-6- ethyl-7formyl-tetrahydronaphthalene was 443 g which had a boiling point of 120C.

The oxime of 1,1,4,4-tetramethyl-6-ethyl-7-formy1- tetrahydronaphthalene was produced by initially dissolving 48.8 g of 1,l,4,4tetramethyl-6-ethyl-7-formyltetrahydronaphthalene in 100 ml of ethanol. The solution was warmed to 50C under agitation until the solution was clear. To the clear ethanol solution was added, over a period of 15 minutes at 50C 16.7 g of hydroxylarnine hydrochloride dissolved in 20 ml of water. To the resulting mixture was added, over a period of 5 minutes at a temperature of 44C, a solution of 12 g of sodium hydroxidedissolved in 16ml of water. The reaction being exothermic, the reaction temperature rose to 56C and than declined. The reaction mixture was agitated for 3/2hours. The temperature of the reaction mixture declined to 25C. g of shaved ice was added, the reaction temperature dropping to 2C. 50 g of solid carbon dioxide (dry ice) in small pieces were added. The reaction temperature dropped to l C, then gradually increased to 23C during agitation over 2% hours. Agitation was terminated and the reaction mixture was permitted to stand overnight. The formed crystals were filtered off on a Buchner funnel. The crystals were washed with 50 ml water portions until neu-.

tral to litmus. The yield was 50 g of 1,] ,4,4- tetramethyl-6-ethyl-7-aldoxime-tetrahydronaphthalene having a melting point of l35l 37C.

To produce 1 l ,4,4-tetramethyl-6-ethyl-7-nitrile-tetrahydronaphthalene, 48.2 g of I,l,4,4-tetramethyl-6- ethyl-7-aldoxime-tetrahydronaphthalene were mixed with 50 g of acetic anhydride. The mixture was heated over a period of minutes to reflux at l40C and the reflux continued for one half hour. The reaction mixture was poured over 120 ml of ice and water. It was agitated and 100 ml of hexane were added. The mixture was separated into an organic part and an aqueous part. The organic part was washed with I00 ml of warm water, then agitated for minutes with 200 ml of a 5% sodium bicarbonate solution. The organic part and aqueous part were then separated. The organic part was washed twice with 50 ml of water. It was neutral to litmus. The solvent was removed by distillation. The reaction product was fractionated through a 6-inch Vigreux column. The yield of l ,l ,4,4-tetramethyl-6-ethyl- 7-nitrile-tetrahydronaphthalene was 32.5 g having a boiling point at l l0-l 12C at 0.4 mm. The product solidified and had a melting point of 4040.5C.

EXAMPLE "I Ambrone Perfume Composition An Ambrone perfume composition is prepared by mixing together the following:

Rose Perfume Composition A rose perfume composition is prepared by mixing together the following:

450 parts Rhodinol 90 parts Rose Geranium Oil, Terpenelcss 50 parts Aldehyde C l0 parts Citral 5 parts I ,l ,4.4-Tetramcthyl-6-Ethyl-7-Nitrile- 'Ictrahydronaphthalene 5 parts l,l,4,4,6-Pcntamethyl-7-Nitrile- Tctrahydronaphthalcne 5 parts Musk Ketonc 20 pans C innamic Alcohol 200 parts Rose Absolute I65 parts Phcnylethyl Propionate L000 parts EXAMPLE v Lavender Perfume Composition A Lavender perfume composition is prepared by mixing together the following:

20 parts Oleoresin Orris Root Florentine Food Grade 25 parts Oil Thyme White N.F. Extra 30 parts Oil Patchouly Singapore 30 parts Bomeol 40 parts 50% solution Oak Moss Absolute 40 parts Heliotropin 50 parts Oil Geranium Al en'an Extra 30 parts l l ,4,4 Tetramet yl-6-Ethyl-7-NitriIe Tetrahydronaphthalene 30 parts Musk Tibetine parts Oil Rosemary Extra 200 art. Oil Bergamot Natural 430 gm; Oil Lavender |,000 parts EXAMPLE Vl- Musk Perfume Composition A Musk perfume composition is prepared by mixing together the following:

EXAMPLE VII Sachet Powder A sachet powder containing no perfume component other than one or a mixture of two novel nitrile tegrahydronaphthalenes of this invention may be prepared by mixing intimately:

50 parts of one or a mixture of two novel nitrile tegrahydronaphthalenes with:

50 parts of talcum powder or kaolin or any diatomaceous earth.

What is claimed is:

l. A composition for use in perfumes comprising at least A by weight of a tetramethyl-alkyI-nitrile-tetrahydronaphthalene and at least 1% by weight of a component which modifies the olfactory properties of said compound, said tetramethylalkyl-nitrile-tetrahydronaphthalene having the formula:

in which R is methyl or ethyl.

2. A composition in accordance with claim 1 in which the compound is l,l,4,4,6-pentamethyl-7- nitrile-tetrahydronaphthalene.

3. A composition in accordance with claim 1 in which the compound is l,l,4,4-tetramethyl-6-ethyl-7- nitrile-tetrahydronaphthalene.

UNITED STATES PATENT OFFICE CTIMCATE 0F COECTlON Patent No. 5,910, 55 Dated October 7. 1975 Inventor(s) Kurt K117 ka It is certified that error appears in the above-identified patent Q and that said Letters Patent are hereby corrected as shown below:

The title of the invention on the first page and in Column 1 should read as follows:

I ,l L, +-TETRAMETHYL-ALKYL-NITRILE-TETRAHYDRONAPHTHALENE PERFUME COMPOSITIONS Column .2, lines &8-65, the formula should read as shown below:

4, I C11. 5 CH- /Ch :l F U l 5 i 1 Q 1 9 all; a C NOE NaCl F// I" f I l:

I I ii Column 5, line 21, "M0 should read ---15o Column 6, line 50, correct the spelling of "exothermic".

Column 7, line 28, insert a degree sign after IIZ Signed and Salad this twenty-third Day of March 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ufParents and Trademarks 

1. A COMPOSITION FOR USE IN PERFUMES COMPRISING AT LEAST 1/4 % BY WEIGHT OF A TETRAMETHYL-ALKYL-NITRILE-TETRAHYDRONAPHTHALENE AND AT LEAST 1% BY WEIGHT OF A COMPONENT WHICH MODIFIES THE OLFACTORY PROPERTIES OF SAID COMPOUND, SAID TETRAMETHYLALKYL-NITRILE-TETRAHYDRONAPTHALENE HAVING THE FORMULA:
 2. A composition in accordance with claim 1 in which the compound is 1,1,4,4,6-pentamethyl-7-nitrile-tetrahydronaphthalene.
 3. A composition in accordance with claim 1 in which the compound is 1,1,4,4-tetramethyl-6-ethyl-7-nitrile-tetrahydronaphthalene. 